P
US8927786B2ActiveUtilityPatentIndex 62

Ethanol manufacturing process over catalyst having improved radial crush strength

Assignee: ZHOU ZHENHUAPriority: Mar 13, 2012Filed: Mar 13, 2012Granted: Jan 6, 2015
Est. expiryMar 13, 2032(~5.7 yrs left)· nominal 20-yr term from priority
Inventors:ZHOU ZHENHUADUFF EMILYKUMAR DHEERAJWEINER HEIKO
B01J 35/37C07C 29/149B01J 23/626B01J 37/10B01J 21/08B01J 23/14B01J 23/42B01J 23/44B01J 23/745B01J 23/75B01J 23/8906B01J 23/8913B01J 23/8993B01J 37/0207B01J 35/613B01J 35/615B01J 21/04
62
PatentIndex Score
3
Cited by
131
References
32
Claims

Abstract

Acetic acid is hydrogenation in the presence of a catalyst comprising one or more active metals on a silica support, wherein the catalyst has a radial crush strength of at least 4 N/mm. The one or more active metals may include cobalt, copper, gold, iron, nickel, palladium, platinum, iridium, osmium, rhenium, rhodium, ruthenium, tin, zinc, lanthanum, cerium, manganese, chromium, vanadium, molybdenum and mixtures thereof. Radial crush strength may be improved by steam treating the catalyst support prior to the loading of the one or more active metals.

Claims

exact text as granted — not AI-modified
We claim: 
     
       1. A process for producing ethanol, comprising:
 hydrogenating acetic acid in a reactor in the presence of a catalyst comprising one or more active metals on a silica support, wherein the catalyst has a radial crush strength of at least 4 N/mm. 
 
     
     
       2. The process of  claim 1 , wherein the radial crush strength is from 4 N/mm to 12 N/mm. 
     
     
       3. The process of  claim 1 , wherein the silica support has an average particle size from 0.01 to 1.0 cm. 
     
     
       4. The process of  claim 1 , wherein the support material has a surface area from 50 to 600 m 2 /g. 
     
     
       5. The process of  claim 1 , wherein pressure drop across the reactor is at least 3 kPa per 1 m. 
     
     
       6. The process of  claim 1 , wherein the silica support is selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica, or mixtures thereof. 
     
     
       7. The process of  claim 1 , wherein the one or more active metals is selected from the group consisting of cobalt, copper, gold, iron, nickel, palladium, platinum, iridium, osmium, rhenium, rhodium, ruthenium, tin, zinc, lanthanum, cerium, manganese, chromium, vanadium, molybdenum and mixtures thereof. 
     
     
       8. The process of  claim 1 , wherein the one or more active metals is selected from the group consisting of palladium, iron, cobalt, platinum, tin and combinations thereof. 
     
     
       9. The process of  claim 1 , wherein acetic acid conversion is greater than 30%. 
     
     
       10. The process of  claim 1 , wherein the hydrogenation conditions include a pressure of 10 kPa to 3000 kPa and a hydrogen to acetic acid molar ratio of greater than 2:1. 
     
     
       11. The process of  claim 1 , wherein the selectivity to ethanol is greater than 60%. 
     
     
       12. The process of  claim 1 , wherein the support material is present in an amount from 25 to 99 wt.%, based on the total weight of the catalyst composition. 
     
     
       13. The process of  claim 1 , wherein the support material further comprises a support modifier, wherein the support modifier is present in an amount from 0.1 to 50 wt.%, based on the total weight of the catalyst composition. 
     
     
       14. The process of  claim 13 , wherein the support modifier is selected from the group consisting of (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof. 
     
     
       15. The process of  claim 13 , wherein the support modifier is calcium metasilicate or calcium oxide. 
     
     
       16. The process of  claim 13 , wherein the support modifier is selected from the group consisting of WO 3 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 , Al 2 O 3 , B 2 O 3 , P 2 O 5 ,Sb 2 O 3 , MoO 3 , Fe 2 O 3 , Cr 2 O 3 , V 2 O 5 , MnO 2 , CuO, Co 2 O 3 , Bi 2 O 3 , and combinations thereof. 
     
     
       17. A process for producing ethanol, comprising:
 hydrogenating acetic acid in a reactor in the presence of a catalyst comprising one or more active metals on a silica support, wherein the silica support is subjected to steam treatment at a temperature above 50° C. for a period of time prior to impregnating the one or more metals on the silica support. 
 
     
     
       18. The process of  claim 17 , wherein the silica support was subjected to steam treatment at a temperature from 50° C. to 300° C. 
     
     
       19. The process of  claim 17 , wherein the steam treatment is from 0.1 to 200 hours. 
     
     
       20. The process of  claim 17 , wherein the silica support comprises at least 0.0001% moisture after treatment and prior to the impregnation of the one or more active metals. 
     
     
       21. The process of  claim 17 , wherein the silica support is further subjected to drying after steam treatment to remove at least some of the moisture in the silica support. 
     
     
       22. The process of  claim 17 , wherein the silica support is selected to the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica, or mixtures thereof. 
     
     
       23. The process of  claim 17 , wherein the one or more active metals is selected from the group consisting of cobalt, copper, gold, iron, nickel, palladium, platinum, iridium, osmium, rhenium, rhodium, ruthenium, tin, zinc, lanthanum, cerium, manganese, chromium, vanadium, molybdenum and mixtures thereof. 
     
     
       24. The process of  claim 17 , wherein the one or more active metals is selected from the group consisting of palladium, iron, cobalt, platinum, tin and combinations thereof. 
     
     
       25. The process of  claim 17 , wherein acetic acid conversion is greater than 30%. 
     
     
       26. The process of  claim 17 , wherein the hydrogenation conditions include a pressure of 10 kPa to 3000 kPa and a hydrogen to acetic acid molar ratio of greater than 2:1. 
     
     
       27. The process of  claim 17 , wherein the selectivity to ethanol is greater than 60%. 
     
     
       28. The process of  claim 17 , wherein the support material is present in an amount from 25 to 99 wt. %, based on the total weight of the catalyst composition. 
     
     
       29. The process of  claim 17 , wherein the support material further comprises a support modifier, wherein the support modifier is present in an amount from 0.1 to 50 wt. %, based on the total weight of the catalyst composition. 
     
     
       30. The process of  claim 29 , wherein the support modifier is selected from the group consisting of (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof. 
     
     
       31. The process of  claim 29 , wherein the support modifier is selected from the group consisting of WO 3 , ZrO 2 , Nb 2 O 5  Ta 2 O 5 , Al 2 O 3 , B 2 O 3 , P 2 O 5  Sb 2 O 3 , MoO 3 , Fe 2 O 3 , Cr 2 O 3 , V 2 O 5 , MnO 2 , CuO, Co 2 O 3 , Bi 2 O 3 , and combinations thereof. 
     
     
       32. A process for producing ethanol, comprising:
 hydrogenating acetic acid in a reactor in the presence of a catalyst comprising silica support subjected to steam treatment, wherein the catalyst has a radial crush strength greater than 50% of a radial crush strength of the silica support prior to steam treatment.

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